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Synthesis characterization, and reactivity of ruthenium maltolato complexes Jonker, Michael J.


The goal of this project was to synthesize and analyze some new ruthenium maltolato complexes as well as to explore their viability as homogeneous catalysts, particularly inaqueous media. The compounds Ru(ma)2(PPh3)2 (1), Ru(ma)2(DMS0)2 (2), Ru(ma)2(COD) (3) and RuH(ma)(C0)(PPh3)2 (4) (where Hma is maltol) were prepared by the interaction of potassium maltolate with RuC12(PPh3)4, RuC12(DMS0)4, [RuC12(COD)ln, andRuHC1(C0)(PPh3)3, respectively. All of these complexes were analyzed by 1H, OH } 13C and, where appropriate, (1H} 31P NMR spectroscopy. In addition, compounds 2 and 3 yielded crystals suitable for study by X-ray crystallography. Comparisons are made between the compounds prepared in this project and other previously synthesized maltolato complexes. The ambidentate nature of dimethyl sulfoxide (DMSO), where it has the ability to coordinate via the sulfur or the oxygen moiety, is also discussed. The DMSO complex, 2, was found to contain two sulfur-bound DMSO ligands, which is the coordination mode expected for a Ru(II) compound. The structure of the DMSO fragment of compound 2 is discussed with respect to structures reported for other DMSO derivatives. The triphenyl phosphine compound, 1, has been found to have the ability to catalyze the dimerization of phenylacetylene to a 1:1 mixture of E- and Z-1,4-diphenylbutenyne.Possible reactions of terminal acetylenes with transition metal complexes are discussed and a mechanism for the dimerization reaction is proposed.

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